CN107042067B - Polysiloxanes-metal-organic framework material hybrid pervaporation composite membrane and its preparation and application - Google Patents

Polysiloxanes-metal-organic framework material hybrid pervaporation composite membrane and its preparation and application Download PDF

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CN107042067B
CN107042067B CN201710371114.0A CN201710371114A CN107042067B CN 107042067 B CN107042067 B CN 107042067B CN 201710371114 A CN201710371114 A CN 201710371114A CN 107042067 B CN107042067 B CN 107042067B
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uio
bpydc
metal
organic framework
membrane
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CN107042067A (en
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姜忠义
于胜楠
潘福生
滕鑫胜
宋伊梦
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Tianjin University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
    • B01D61/362—Pervaporation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • C10G31/11—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by dialysis
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Water Supply & Treatment (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The present invention discloses a kind of polysiloxanes-metal-organic framework material hybrid pervaporation composite membrane, is made of separating layer and supporting layer；Separating layer is with a thickness of 5~15 microns, UiO-67-bpydc nanometers are modified with metal-organic framework material UiO-67-bpydc or copper by dimethyl silicone polymer (PDMS) polymer matrix membrane or submicron particles filler is constituted, and the mass ratio of UiO-67-bpydc and polymer matrix membrane PDMS are 2~8%.By a certain amount of filling agent particle ultrasonic disperse in a solvent, hydroxy-end capped PDMS oligomer and silane coupling agent are added in gained suspension, stirring and dissolving forms casting solution, and catalyst is added；Casting solution is coated in supporting layer upper surface, naturally dry is put into baking oven heat treatment.Permeability of the membrane can be improved in filler, and the selectivity of film is kept using the functional group of itself, to improve membrane separating property.Preparation method of the present invention is simple and easy to operate, and film obtained is used for pervaporation desulfurizing oil process, there is higher separating property.

Description

Polysiloxanes-metal-organic framework material hybrid pervaporation composite membrane and its preparation With application
Technical field
The present invention relates to seperation film and its preparation and application, belong to technical field of membrane separation, specifically, belonging to macromolecule Hybrid separation membrane field.
Background technique
Dimethyl silicone polymer (PDMS) is a kind of macromolecule member material, strong, the permeability high and low temperature performance with hydrophobicity Good, advantage at low cost removes volatile organic matter, alcohol-water separation, organic small-molecule mixture separation in gas separation, water There is relatively broad application in equal fields.PDMS film is weaker due to interacting between polymer segment, be easily swollen in organic solvent, Stability is insufficient, needs to make up by being crosslinked, and being crosslinked can make membrane structure become fine and close, and permeability of the membrane is caused to incur loss.
Metal-organic framework material (MOF) is a kind of novel porous materials, have flourishing cellular structure with it is good adjustable Control property, there is relatively broad application in fields such as absorption, separation, light, electricity, magnetic, catalysis, targeted drug, sensors.By zirconium ion With 4, a kind of entitled UiO-67 of MOF of 4 '-biphenyl dicarboxylic acid ligands composition has the advantages that high stability, gas separation, Liquid small-molecule mixture separation etc. has more application.The ligand of UiO-67 is replaced into bipy 2,2' bipyridyl -5,5 '-two Carboxylic acid (H2Bpydc), can obtain it is a kind of with the UiO-67 isomorphism entitled UiO-67-bpydc of MOF (Chem.Commun., 2014,50, 4810-4812), bipyridyl group has certain activity as a kind of bidentate ligand, can be used in membrane separating process with infiltration Interaction occurs for saturating molecule to improve membrane separating property, or is used for further functional modification.
Summary of the invention
In conjunction with the aforementioned prior art, the present invention proposes a kind of polysiloxanes-metal-organic framework material hybrid pervaporation Composite membrane and its preparation and application.Method provided by the invention is simple and easy to operate, and prepared composite membrane is for pervaporation oil Product sweetening process has higher separating property.
A kind of polysiloxanes proposed by the present invention-metal-organic framework material hybrid pervaporation composite membrane, by separating layer It is formed with supporting layer.The separating layer is had by fine and close polymer matrix membrane PDMS with the metal being dispersed in polymer matrix membrane Machine frame material filler composition, 5~15 microns of thickness；The supporting layer is made of porous ultrafiltration membrane；The metal is organic Frame material filler is that UiO-67-bpydc nanometers or submicron particles, copper modify UiO-67-bpydc nanometers or sub-micron In grain any one or mixtures thereof, UiO-67-bpydc and the macromolecule in the metal-organic framework material filler The mass ratio of membrane matrix PDMS is 2~8%；Described UiO-67-bpydc nanometers or submicron particles are joined by zirconium ion and 2,2 '- Pyridine -5,5 '-dicarboxylates composition；The copper is modified in UiO-67-bpydc nanometers or submicron particles, and copper and zirconium rub Your ratio is 28.2~60.4%；The ultrafiltration membrane is polysulfones, polyether sulfone, any one in polyvinylidene fluoride (PVDF) ultrafiltration membrane, section Staying molecular weight is 10~100kDa.
In the present invention, copper, which modifies UiO-67-bpydc nanometers or submicron particles, to be implemented by solvent thermal process.Specifically For, copper nitrate is mixed by copper with molar ratio (1:3)~(3:1) of zirconium with UiO-67-bpydc, water heating kettle is added, is added molten 12~48h is heated in agent under the conditions of 55~70 DEG C, and copper is made and modifies UiO-67-bpydc filler.The solvent is acetonitrile, Mole is 200~500 times of zirconium.
A kind of polysiloxanes proposed by the present invention-metal-organic framework material hybrid pervaporation composite membrane preparation side Method, step are: under room temperature, a certain amount of metal-organic framework material filler ultrasonic disperse in a solvent is outstanding in gained Hydroxy-end capped PDMS oligomer (1~10Pas of viscosity) and silane coupling agent are added in turbid, stirring and dissolving forms casting solution, In the metal-organic framework material filler mass ratio of UiO-67-bpydc and the hydroxy-end capped PDMS oligomer be 2~ 8%；Catalyst is added into casting solution, accelerates cross-linking reaction；Wherein, solvent, hydroxy-end capped PDMS oligomer, silane Coupling agent, catalyst mass ratio be 1000:(100~500): (20~50): (1~10)；By treated casting solution Coated in supporting layer upper surface, 5~48h is placed at 10~40 DEG C and carries out naturally dry, is then placed in and is preheated to 50~85 DEG C It is gained that baking oven, which is heat-treated 1~10h,.
In the present invention, the solvent be hexane, heptane, in octane any one or mixtures thereof.It is described silane coupled Agent can be tetramethoxy-silicane (TMOS), tetraethoxysilane (TEOS), γ-aminopropyltrimethoxysilane (APTMS), In gamma-aminopropyl-triethoxy-silane (APTES) any one or mixtures thereof, preferably APTMS.The catalyst can be Organotin catalysts (such as T-12) or organic bismuth catalyst (such as DY-20), preferably organotin catalysts T-12.
In the present invention, the connection pyrrole of metal-organic framework material filler UiO-67-bpydc or copper modification UiO-67-bpydc π complexing can occur with the organic sulphur impurity of thiophene-based and interact for piperidinyl group, keep the selectivity of film；By influencing PDMS macromolecule The warm-up movement and spatial arrangement state of segment improve permeability of the membrane, to improve membrane separating property.
A kind of polysiloxanes that the method through the invention is prepared-metal-organic framework material hybridized osmotic steams It sends out composite membrane and is used for pervaporation desulfurizing oil process, material liquid is analog gasoline, is made of normal octane and thiophene；In operation temperature In 30~60 DEG C of degree, material liquid under conditions of sulfur nutrient 0.05~0.08%, raw material flow velocity 40L/h, permeation flux is 4.9~16.7kg/ (m2H), enrichment factor is 3.4~4.6.Compared with blank control film, the permeation flux of film improves 74%, Enrichment factor improves 10%.
Detailed description of the invention
Fig. 1 is the modification UiO-67-bpydc filler TEM image of copper made from embodiment 2.
Fig. 2 is UiO-67-bpydc filler made from embodiment 5 and matrix mass ratio is 4% polysiloxanes-metal Organic framework materials hybrid pervaporation composite membrane section (amplification factor 2000) SEM image.
Fig. 3 is the part UiO-67-bpydc and matrix in the modification UiO-67-bpydc filler of copper made from embodiment 8 Mass ratio is 4% polysiloxanes-metal-organic framework material hybrid pervaporation composite membrane section (amplification factor 2000) SEM Image.
Specific embodiment
Implementation process of the invention is illustrated below by way of comparative example and embodiment, and providing comparative example and embodiment is to manage The convenience of solution, be not intended to limit the present invention the range covered.Those skilled in the art is under the inspiration of the present invention, main in the present invention The change that purport is made in the range of covering still in the scope of the present invention within.
Comparative example 1: preparation blank control film, comprising the following steps:
Under room temperature, hydroxy-end capped PDMS oligomer (viscosity 6Pas) and γ-aminopropyl front three are added in heptane Oxysilane (APTMS), stirring and dissolving, then, be added organotin catalysts T-12, heptane, hydroxy-end capped PDMS oligomer, The mass ratio of APTMS, T-12 are 1000:220:42:10, form casting solution, by casting solution coated in molecular cut off 50kDa's Polyvinylidene fluoride (PVDF) ultrafiltration membrane upper surface places 9.5h at 25 DEG C and carries out naturally dry, is then placed in and is preheated to 85 DEG C of baking oven heat 1h is handled, blank control film is made.
By film made from comparative example 1 in 40 DEG C of operation temperature, material liquid sulfur nutrient 0.05%, raw material flow velocity Pervaporation desulfurizing oil performance evaluation is carried out under conditions of 40L/h, and the permeation flux of film is calculated using formula J=Q/ (At), Wherein, it is the operating time that Q, which is that collected permeate quality, A are the effective area of film, t in certain operating time,；Use formula β=ωP/ωFCalculate the enrichment factor of film, wherein ωPIt is sulfur nutrient in permeate, ωFIt is sulphur quality point in material liquid Number.Evaluation result is permeation flux 4.6kg/ (m2H), enrichment factor 3.9.
Embodiment 1: the copper of preparation load capacity (molar ratio of copper and zirconium) 28.2% modifies UiO-67-bpydc nanometers or sub- Micron particles, step are: copper nitrate being mixed by copper with the molar ratio 1:3 of zirconium with UiO-67-bpydc and is put into water heating kettle, is added Acetonitrile (mole be zirconium 500 times) heats 12h at 70 DEG C, and the copper modification UiO-67-bpydc that load capacity 28.2% is made receives Rice or submicron particles.
Embodiment 2: the copper of preparation load capacity 38.6%, which modifies UiO-67-bpydc nanometers or submicron particles, step, is: Copper nitrate is mixed by copper with the molar ratio 1:1 of zirconium with UiO-67-bpydc and is put into water heating kettle, acetonitrile is added, and (mole is zirconium 300 times), it heats at 65 DEG C and the copper of load capacity 38.6% is made for 24 hours modifies UiO-67-bpydc nanometers or submicron particles, TEM image is as shown in Figure 1.
Embodiment 3: the copper of preparation load capacity 60.4%, which modifies UiO-67-bpydc nanometers or submicron particles, step, is: Copper nitrate is mixed by copper with the molar ratio 3:1 of zirconium with UiO-67-bpydc and is put into water heating kettle, acetonitrile is added, and (mole is zirconium 200 times), 48h is heated at 55 DEG C, and the copper that load capacity 60.4% is made modifies UiO-67-bpydc nanometers or submicron particles.
Embodiment 4: the mass ratio for preparing UiO-67-bpydc nanometers or submicron particles and polymer matrix membrane PDMS is 2% hybridized film, comprising the following steps:
Under room temperature, a certain amount of UiO-67-bpydc filling agent particle ultrasonic disperse in hexane, it is suspended in gained Hydroxy-end capped PDMS oligomer (viscosity 4Pas) and APTMS are added in liquid, stirring and dissolving forms casting solution, filler UiO- The mass ratio of 67-bpydc and hydroxy-end capped PDMS oligomer is 2%.Organotin catalysts T-12 is added, it is hexane, hydroxy-end capped PDMS oligomer, APTMS, T-12 mass ratio be 1000:100:20:8.Treated casting solution is coated in retention point Son measures the polyvinylidene fluoride (PVDF) ultrafiltration membrane upper surface of 10kDa, places 9h at 27 DEG C and carries out naturally dry, is then placed in and is preheated to 56 DEG C Baking oven be heat-treated 9h, be made hybridized film.By the film in 40 DEG C of operation temperature, material liquid sulfur nutrient 0.05%, raw material Pervaporation desulfurizing oil performance evaluation is carried out under conditions of flow velocity 40L/h, evaluation result is permeation flux 4.9kg/ (m2· H), enrichment factor 4.4.
Embodiment 5: the mass ratio for preparing UiO-67-bpydc nanometers or submicron particles and polymer matrix membrane PDMS is 4% hybridized film, comprising the following steps:
Under room temperature, a certain amount of UiO-67-bpydc filling agent particle ultrasonic disperse in heptane, it is suspended in gained Hydroxy-end capped PDMS oligomer (viscosity 8Pas) and APTMS are added in liquid, stirring and dissolving forms casting solution, filler UiO- The mass ratio of 67-bpydc and hydroxy-end capped PDMS oligomer is 4%.Organotin catalysts T-12 is added, it is heptane, hydroxy-end capped PDMS oligomer, APTMS, T-12 mass ratio be 1000:440:27:6.Treated casting solution is coated in retention point Son measures the polyvinylidene fluoride (PVDF) ultrafiltration membrane upper surface of 30kDa, places 16h at 15 DEG C and carries out naturally dry, is then placed in and is preheated to 50 DEG C baking oven be heat-treated 10h, hybridized film is made, the SEM image of section is as shown in Figure 2.
By the film in 40 DEG C of operation temperature, material liquid under conditions of sulfur nutrient 0.05%, raw material flow velocity 40L/h Pervaporation desulfurizing oil performance evaluation is carried out, evaluation result is permeation flux 5.2kg/ (m2H), enrichment factor 4.6.
Embodiment 6: the mass ratio for preparing UiO-67-bpydc nanometers or submicron particles and polymer matrix membrane PDMS is 8% hybridized film, comprising the following steps:
Under room temperature, a certain amount of UiO-67-bpydc filling agent particle ultrasonic disperse in octane, it is suspended in gained Hydroxy-end capped PDMS oligomer (viscosity 7Pas) and APTMS are added in liquid, stirring and dissolving forms casting solution, filler UiO- The mass ratio of 67-bpydc and hydroxy-end capped PDMS oligomer is 8%.Organotin catalysts T-12 is added, it is octane, hydroxy-end capped PDMS oligomer, APTMS, T-12 mass ratio be 1000:460:50:4.Treated casting solution is coated in retention point The polysulfone ultrafiltration membrane upper surface of son amount 20kDa places 5h at 40 DEG C and carries out naturally dry, is then placed in and is preheated to 85 DEG C of baking oven It is heat-treated 1h, hybridized film is made.By the film in 40 DEG C of operation temperature, material liquid sulfur nutrient 0.05%, raw material flow velocity Pervaporation desulfurizing oil performance evaluation is carried out under conditions of 40L/h, evaluation result is permeation flux 5.0kg/ (m2H), rich Collect the factor 3.9.
Embodiment 7: the part UiO-67-bpydc in copper modification UiO-67-bpydc filler and polymeric membrane base are prepared The mass ratio of matter PDMS is 4% hybridized film (filler is made in embodiment 1), comprising the following steps:
Under room temperature, filling agent particle obtained ultrasonic disperse in hexane in a certain amount of embodiment 1, it is outstanding in gained It is added hydroxy-end capped PDMS oligomer (viscosity 10Pas) and APTMS in turbid, stirring and dissolving forms casting solution, in filler The part UiO-67-bpydc and the mass ratio of hydroxy-end capped PDMS oligomer be 4%.Organotin catalysts T-12 is added, oneself Alkane, hydroxy-end capped PDMS oligomer, APTMS, T-12 mass ratio be 1000:350:30:1.By treated casting solution Poly (ether-sulfone) ultrafiltration membrane upper surface coated in molecular cut off 100kDa places 7.5h at 32 DEG C and carries out naturally dry, then puts The baking oven heat treatment 2h for entering to be preheated to 80 DEG C, is made hybridized film.By the film in 40 DEG C of operation temperature, material liquid sulfur nutrient 0.05%, pervaporation desulfurizing oil performance evaluation is carried out under conditions of raw material flow velocity 40L/h, evaluation result is permeation flux 5.4kg/(m2H), enrichment factor 4.5.
Embodiment 8: the part UiO-67-bpydc in copper modification UiO-67-bpydc filler and polymeric membrane base are prepared The mass ratio of matter PDMS is 4% hybridized film (filler is made in example 2), comprising the following steps:
Under room temperature, filling agent particle ultrasonic disperse in heptane obtained in a certain amount of embodiment 2, it is outstanding in gained It is added hydroxy-end capped PDMS oligomer (viscosity 5Pas) and APTMS in turbid, stirring and dissolving forms casting solution, in filler The part UiO-67-bpydc and the mass ratio of hydroxy-end capped PDMS oligomer be 4%.Organotin catalysts T-12, heptan is added Alkane, hydroxy-end capped PDMS oligomer, APTMS, T-12 mass ratio be 1000:300:23:3.By treated casting solution Polyvinylidene fluoride (PVDF) ultrafiltration membrane upper surface coated in molecular cut off 30kDa places 8h at 30 DEG C and carries out naturally dry, then puts The baking oven heat treatment 4h for entering to be preheated to 75 DEG C, is made hybridized film, the SEM image of section is as shown in Figure 3.
By the film in 40 DEG C of operation temperature, material liquid under conditions of sulfur nutrient 0.05%, raw material flow velocity 40L/h Pervaporation desulfurizing oil performance evaluation is carried out, evaluation result is permeation flux 8.1kg/ (m2H), enrichment factor 4.2.
Embodiment 9: the part UiO-67-bpydc in copper modification UiO-67-bpydc filler and polymeric membrane base are prepared The mass ratio of matter PDMS is 4% hybridized film (filler is made in embodiment 3), comprising the following steps:
Under room temperature, filling agent particle ultrasonic disperse in octane obtained in a certain amount of embodiment 3, it is outstanding in gained It is added hydroxy-end capped PDMS oligomer (viscosity 1Pas) and APTMS in turbid, stirring and dissolving forms casting solution, in filler The part UiO-67-bpydc and the mass ratio of hydroxy-end capped PDMS oligomer be 4%.Organotin catalysts T-12 is added, it is pungent Alkane, hydroxy-end capped PDMS oligomer, APTMS, T-12 mass ratio be 1000:500:30:7.By treated casting solution Poly (ether-sulfone) ultrafiltration membrane upper surface coated in molecular cut off 50kDa places 48h at 10 DEG C and carries out naturally dry, is then placed in It is preheated to 63 DEG C of baking oven heat treatment 8h, hybridized film is made.By the film in 40 DEG C of operation temperature, material liquid sulfur nutrient 0.05%, pervaporation desulfurizing oil performance evaluation is carried out under conditions of raw material flow velocity 40L/h, evaluation result is permeation flux 5.0kg/(m2H), enrichment factor 4.3.
Embodiment 10: by hybridized film made from embodiment 8 in 30 DEG C of operation temperature, material liquid sulfur nutrient 0.05%, pervaporation desulfurizing oil performance evaluation is carried out under conditions of raw material flow velocity 40L/h, evaluation result is permeation flux 5.6kg/(m2H), enrichment factor 4.5.
Embodiment 11: by hybridized film made from embodiment 8 in 60 DEG C of operation temperature, material liquid sulfur nutrient 0.05%, pervaporation desulfurizing oil performance evaluation is carried out under conditions of raw material flow velocity 40L/h, evaluation result is permeation flux 16.7kg/(m2H), enrichment factor 3.4.
Embodiment 12: by hybridized film made from embodiment 8 in 40 DEG C of operation temperature, material liquid sulfur nutrient 0.08%, pervaporation desulfurizing oil performance evaluation is carried out under conditions of raw material flow velocity 40L/h, evaluation result is permeation flux 9.1kg/(m2H), enrichment factor 3.6.
To sum up, in preparation method of the present invention, permeability of the membrane is can be improved in filler, and is kept using the functional group of itself The selectivity of film, to improve membrane separating property.Membrane preparation method provided by the invention is simple and easy to operate, and film obtained is for seeping Evaporation desulfurizing oil process thoroughly, there is higher separating property.

Claims (5)

1. a kind of polysiloxanes-metal-organic framework material hybrid pervaporation composite membrane, is made of separating layer and supporting layer；Institute Supporting layer is stated to be made of porous ultrafiltration membrane；It is characterized by:
The separating layer with a thickness of 5~15 microns, by fine and close polymer matrix membrane and be dispersed in polymer matrix membrane Metal-organic framework material filler composition；
The polymer matrix membrane is PDMS；The metal-organic framework material filler is UiO-67-bpydc nanometers or sub-micro Rice grain and copper modify or mixtures thereof any one in UiO-67-bpydc nanometers or submicron particles；The metal is organic The mass ratio of the UiO-67-bpydc and PDMS is 2~8% in frame material filler；
Described UiO-67-bpydc nanometers or submicron particles are by zirconium ion and bipy 2,2' bipyridyl -5,5 '-dicarboxylates group At；The copper is modified in UiO-67-bpydc nanometers or submicron particles, and the molar ratio of copper and zirconium is 28.2~60.4%；
The ultrafiltration membrane is polysulfones, polyether sulfone, any one in polyvinylidene fluoride (PVDF) ultrafiltration membrane, the retention molecule of the ultrafiltration membrane Amount is 10~100kDa.
2. a kind of polysiloxanes as described in claim 1-metal-organic framework material hybrid pervaporation composite membrane preparation side Method, which comprises the following steps:
Under room temperature, a certain amount of metal-organic framework material filler ultrasonic disperse in a solvent, in gained suspension Hydroxy-end capped PDMS oligomer and silane coupling agent is added, the viscosity of the hydroxy-end capped PDMS oligomer is 1~10Pas, Stirring and dissolving forms casting solution, and UiO-67-bpydc is low with the hydroxy-end capped PDMS in metal-organic framework material filler The mass ratio of polymers is 2~8%；Catalyst is added into casting solution, accelerates cross-linking reaction；Wherein, solvent, hydroxyl envelope Holding the mass ratio of PDMS oligomer, silane coupling agent, catalyst is: 1000:(100~500): (20~50): (1~10)；It will Treated casting solution is coated in supporting layer upper surface, places 5~48h at 10~40 DEG C and carries out naturally dry, then puts Enter to be preheated to 50~85 DEG C of baking oven and is heat-treated 1~10h as gained.
3. polysiloxanes-metal-organic framework material hybrid pervaporation composite membrane preparation method according to claim 2, Wherein:
The solvent be hexane, heptane, in octane any one or mixtures thereof；
The silane coupling agent is tetramethoxy-silicane, tetraethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyl In triethoxysilane any one or mixtures thereof；
The catalyst is organotin catalysts or organic bismuth catalyst.
4. polysiloxanes-metal-organic framework material hybrid pervaporation composite membrane preparation method according to claim 2, Wherein, the silane coupling agent is γ-aminopropyltrimethoxysilane；The catalyst is organotin catalysts.
5. a kind of application of polysiloxanes as described in claim 1-metal-organic framework material hybrid pervaporation composite membrane, It is characterized in that, film as described in claim 1 is used for pervaporation desulfurizing oil process, material liquid is analog gasoline, by just Octane and thiophene form；Sulfur nutrient 0.05~0.08%, raw material flow velocity in 30~60 DEG C of operation temperature, material liquid Under conditions of 40L/h, permeation flux is 4.9~16.7kg/ (m2H), enrichment factor is 3.4~4.6.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110508166B (en) * 2019-07-23 2021-10-12 西北大学 Surface metal ion modified silicon rubber desulfurization film and preparation method and application thereof
CN111087635A (en) * 2019-12-26 2020-05-01 上海工程技术大学 PDMS @ F-MOF composite film for friction nano-generator and preparation method thereof
CN114163817B (en) * 2021-11-10 2022-08-05 浙江大学 Slow-release antibacterial film and preparation method thereof
CN116262210B (en) * 2021-12-14 2024-03-01 泰州九润环保科技有限公司 High-selectivity pervaporation gasoline desulfurization membrane and preparation method thereof
CN114159987B (en) * 2021-12-14 2023-05-23 泰州九润环保科技有限公司 Pervaporation gasoline desulfurization membrane and preparation method thereof
CN114288870A (en) * 2021-12-31 2022-04-08 武汉智宏思博环保科技有限公司 Synthetic method of MOFs-organic silicon hybrid membrane
CN115926462B (en) * 2022-07-19 2023-10-31 南昌大学 Preparation method of zirconium-based metal organic framework molded body and application of zirconium-based metal organic framework molded body in food safety detection

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101693168A (en) * 2009-10-14 2010-04-14 大连理工大学 Method for preparing metal organic framework film
CN103846013A (en) * 2012-12-05 2014-06-11 中国科学院大连化学物理研究所 Porous material-polymer gas separation composite membrane
CN104001426A (en) * 2014-05-29 2014-08-27 北京工业大学 Preparation method of high dispersion metal-organic framework (MOF)/organic hybrid priority alcohol through composite membrane
CN104117290A (en) * 2014-07-03 2014-10-29 北京工业大学 Preparation method of MOFs tube type hybrid membrane for separating aromatic hydrocarbons/alkyl hydrocarbons
EP3031513A1 (en) * 2014-12-11 2016-06-15 Vaillant GmbH Heat and moisture exchanger

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2928562A4 (en) * 2012-12-06 2016-06-22 Stealth Peptides Int Inc Peptide therapeutics and methods for using same
JP2017500204A (en) * 2013-10-16 2017-01-05 サビック グローバル テクノロジーズ ビー．ブイ． Mixed matrix polymer membrane

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101693168A (en) * 2009-10-14 2010-04-14 大连理工大学 Method for preparing metal organic framework film
CN103846013A (en) * 2012-12-05 2014-06-11 中国科学院大连化学物理研究所 Porous material-polymer gas separation composite membrane
CN104001426A (en) * 2014-05-29 2014-08-27 北京工业大学 Preparation method of high dispersion metal-organic framework (MOF)/organic hybrid priority alcohol through composite membrane
CN104117290A (en) * 2014-07-03 2014-10-29 北京工业大学 Preparation method of MOFs tube type hybrid membrane for separating aromatic hydrocarbons/alkyl hydrocarbons
EP3031513A1 (en) * 2014-12-11 2016-06-15 Vaillant GmbH Heat and moisture exchanger

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